CN105143503A - Methods of low temperature deposition of ceramic thin films - Google Patents

Methods of low temperature deposition of ceramic thin films Download PDF

Info

Publication number
CN105143503A
CN105143503A CN201480010010.1A CN201480010010A CN105143503A CN 105143503 A CN105143503 A CN 105143503A CN 201480010010 A CN201480010010 A CN 201480010010A CN 105143503 A CN105143503 A CN 105143503A
Authority
CN
China
Prior art keywords
deposition
ald
technique
precursors
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201480010010.1A
Other languages
Chinese (zh)
Inventor
普拉萨德·纳哈·加吉尔
彼得·约瑟夫·杜绍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CN105143503A publication Critical patent/CN105143503A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
    • C23C16/14—Deposition of only one other metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45514—Mixing in close vicinity to the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02115—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material being carbon, e.g. alpha-C, diamond or hydrogen doped carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02167—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02529—Silicon carbide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Abstract

A method is provided for low temperature deposition of ceramic thin films of carbides, nitrides and mixed phases such as carbo-nitrides by atomic layer deposition (ALD), nano-layer deposition (NLD), and chemical vapor deposition (CVD). The deposition chemistries employ combinations of precursors to affect thin film processes at substantially lower temperatures than current deposition processes of thin films of boron (B) carbides, nitrogen (N), nitrides, carbonitrides of silicon (Si), carbon (C), germanium (Ge), phosphorus (P), arsenic (As), oxygen (O), sulfur (S), and selenium (S) on substrates. The inventive ALD and corresponding NLD and CVD process methods provide lower temperature deposition of various thin films comprising elements from the group B, C, Si, Ge, N, P, As and O, S and Se. The reactive precursor combinations are selected on the basis of reactivity towards one another as determined by the variation of Gibb's free energy (delta G) with respect to deposition temperature.

Description

Ceramic membrane low temperature deposition method
the cross reference of related application
The application advocate to submit on December 21st, 2012 sequence number be the right of priority of the U.S. Provisional Patent Application of 61/745,523, accordingly, its content is incorporated to by way of reference.
Technical field
The present invention relates generally to the deposition method of film, particularly relate to by ald (ALD), the carbide of nanometer layer deposition process (NLD) and chemical vapour deposition (CVD) method, the low temperature deposition method of the ceramic membrane that the mixed phase of nitride and such as carbonitride is formed.
Background technology
The film be made up of carbide, nitride and the carbonitride that is made up of silicon, germanium, boron and its mixed phase is widely used in high temperature, high power electronic device, the sensor worked under severe environment, anticorrosive and anti abrasive coating, photodiode (LED) manufactures.The method that the thin film deposition processes of these materials generally adopts comprises sputtering, physical vapor deposition (PVD), chemical vapour deposition (CVD) and ald (ALD) and other various method relating to plasma deposition.But, in the deposition method of these films, chemical vapour deposition (CVD) and ald (ALD), due to the various advantages had in film quality, moiety, homogeneity, adhesivity and large area coverage, thus become current main stream approach.
The CVD technique of industrial extensive employing is a kind of technique relying on flux.Under kinetics restriction state, CVD technique is equally also responsive to underlayer temperature.But CVD technique can operate under high deposition rate (from several micro-m/h to hundreds of micro-m/h), and this is well-adapted in industrial environment usually.On the other hand, compared with CVD technique, ALD technique has some key advantages in uniformity of film, flux isolated footing, is not therefore subject to the impact of substrate dimension and shape.In addition, ALD technique additionally provides the coating of submicron order substrate feature, and reflects the lower process deposits temperature on precursor surface catalysis interaction basis in some cases.But, compared with CVD technique, ALD but perplex by lower film deposition rate (can be an order of magnitude or lower).
In addition, in typical CVD technique, two or more reactant gases (precursor) mix, and flow through the heated substrate contributing to realizing extensive deposition.Only have when precursor does not show the tendency of carrying out pre-reaction when mixing, such setting is only feasible.But in some cases, if this precursor shows strong reactivity to each other, before they arrive substrate surface, these gases must be separated, but must distribute equably on substrate after arriving substrate simultaneously.And to carry out designing and operate two CVD reactor that sprays according to such requirement be quite complicated.
In the ald process, this precursor is injected in processing volume successively, this precursor is scattered between sweeping gas.For practical purposes, sweeping gas can be the gas of the chemical reaction of any not active participate thin film deposition.In the ald process, due to the independence of its flux, usually do not need the dispersed of reactant.Therefore, the simple separation of reactant injector is just enough to set up ALD technique.These advantages allow to screen high reactivity precursor in the ald process, and the operation of this screening in CVD technique is quite complicated.In fact, people endeavour to seek always or in the urgent need to the precursor of height reactive behavior to each other to set up effective ALD thin-film technique.
In typical ALD method, two or more reactant gas in order pulse being placed in the heated substrate in treatment chamber.This reactant gases pulse by purge gas realize be separated or by two kinds of reactant gas pulse dispersal in constant gaseous purge stream.But in CVD technique, the heated substrate being placed in treatment chamber then will make the flowing of reactant carry out with the optional flowing as the sweeping gas of carrier gas simultaneously.
Existing SiCCVD technique follows this path to a great extent.Such as, the people such as K.Fujihira are at " crystal growth magazine " the 255th volume, and 136 pages (2003), demonstrate and adopt silane (SiH at 1300 DEG C 4) and propane (C 3h 8) prepare the high efficiency CVD technique of 4H carborundum films.The people such as Stoldt adopt 1,3-bis-sila butane (SiH 3-CH 2-SiH 2-CH 3) develop single precursor, the CVD technique of low temperature (800-1000 DEG C) SiC film, be described in " sensor and performer A ", 97-98 rolls up, 410 pages (2002).But the people such as Sone describe the single precursor CVDSiC technique adopting METHYL TRICHLORO SILANE to operate at 1300 DEG C, (MTS:CH 3-SiCl 3), be published in " crystal growth magazine " the 219th volume, 245 pages (2000).It is evident that the deposition reaction of usual SiC film is carried out at temperature is more than 1000 DEG C at this.As everyone knows, containing BN, B 4c and Si 3n 4the deposition reaction of ceramic membrane can carry out in similar temperature range.
Application number be 2012/0122302 United States Patent (USP) describe employing 1,3,5-Tutofusin tris (C 3si 3h 12) the plasmaassisted low temperature SiC depositing operation that carries out at 200 DEG C as precursor.But the SiC film as deposition needs to carry out further densification at 600 DEG C.Application number is describe in the United States Patent (USP) of 2012/0177841 to adopt silicon tetrachloride (SiCl 4) as the repeated deposition technique in silicon source, by trimethyl aluminium [(CH 3) 3aI] reduce silicon source consumption, in order to reduce mixture Si in product film with Cement Composite Treated by Plasma subsequently or temperature lower than the thermal treatment of 600 DEG C xc yh z(0<z<16) content of H.Application number is in the United States Patent (USP) of 2012/0214318Al, and this adopts two-chloro-tetramethyl-disilane [Si under inventors describing the temperature within the scope of 100-400 DEG C 2cl 2(CH 3) 4] and the hydrogen plasmaassisted ALD technique of carrying out, the product film containing SiC compound can be obtained, but between carbon silicon, ratio not yet confirms.If the patent No. is RE42, in the process described by the United States Patent (USP) of 887, this inventor adopts dichlorosilane (Si 2cl 2) and acetylene (C 2h 2) react in the hydrogen of 900 DEG C, obtain SiC film.
The patent No. is 7,901, and the United States Patent (USP) of 508 describes and in main hydrogen stream, uses halohydrocarbon as chlorine source under the underlayer temperature of 1600 DEG C, with the silane (SiH as silicon source 4) and as the propane (C of carbon source 3h 8) combine.In Si-H-C-CI system, add halohydrocarbon add HCl (hydrochloric acid) gas than in its system and have more operational advantage, this system known is by suppressing silicon nucleation to improve the sedimentation velocity of SiC at a higher temperature.Known silicon nucleation is highly disadvantageous to SiC film quality in defect concentration.
When BN thin film deposition, the technique generally adopted is by BCI at higher than the temperature of 1000 DEG C 3with NH 3be incorporated into line operate.The slightly novel boron nitride layer depositing operation now developed is at 1000 DEG C of temperature, adopt ring-type integrated chemical precursor s-nitrine borine (B 3h 3n 3) carry out operating.On the other hand, radio frequency (RF) or microwave (MW) plasma body is used recently and with methane (CH 4) and nitrogen N 2a kind of possible superhard material carbon-nitride (C is deposited as nitrogenous source 3n 4).
Owing to needing high treatment temp, although have higher business and technological value, the selection of these film-substrate also can only be confined to pottery, silicon, quartz.In addition, higher treatment temp usually can cause some serious operational deficiencies, often limits its commercial applications.And for the finished product, high service temperature will cause the high defect concentration of the performance of heavily stressed, the serious reduction equipment of film.In addition, the mutual diffusion of layer, substrate warpage, to be difficultly combined with other films and the existence of impurity inclusion all can become a series of serious problems under high-temperature operation.In operation of equipment, the consumption of the problem of high power consumption, the selectional restriction for the treatment of chamber construction material and its weather resistance, airflow stability, precursor and go out water treatment and both increase cost and complicacy.
Therefore, be necessary to develop CVD and the ALD technique of low temperature, for the preparation of the ceramic membrane be selected from by the elementary composition various compositions of B, N and C, Si, Ge.The element combinations forming film includes, but are not limited to SiC, BN, B 4c, SiCXN y, Si 3n 4, Si xge (1-X), Si xge (1-X)c, GeC etc.
Summary of the invention
For the low temperature deposition method of ceramic membrane coating be made up of carbide, nitride and its mixed phase, the method comprises and adopts the combination of reactive behavior precursor to determine that deposition chemistries is to affect the temperature required of substrate surface thin film deposition; Substrate is loaded in treatment chamber; Adjust one or more processing parameter, comprise underlayer temperature, chamber pressure and chamber temp; Start deposition cycle; Determine whether film coating reaches pre-determined thickness, and repeat this deposition cycle until reach predetermined thickness; Wherein this deposition is realized by ald (ALD), nanolayer deposition (NLD) or chemical vapour deposition (CVD); And wherein the composition of reactive behavior precursor is screened by the reactive behavior between each reactive behavior precursor of determination of changing relative to the Gibbs free energy (AG) of depositing temperature in chamber.
The method comprises boron (B) carbide, nitrogen (N), nitride, siliceous (Si), carbon (C), germanium (Ge), phosphorus (P), arsenic (as), the membrane deposition method of the carbonitride of oxygen (O), sulphur (S) and selenium (S).The reaction Gibbs free energy of higher negative value defines the basis of screening reactive behavior precursor composition.
Accompanying drawing explanation
Figure 1A shows the substrate that has surface-OH groups, and this group formed by chemical absorbed water in environment, and as CO and CO 2other molecule can not form strong chemical bond with surface, only can be physically adsorbed;
Figure 1B illustrate Cl with from TiCl 4the exchange of the surperficial H of chemisorption and the formation of O-Ti key;
Fig. 1 C illustrates in an ALD technique, the TiCl of chemisorption 3with water (H 2o) molecularity forms TiO 2reaction;
Fig. 2 A describes a typical ALD circulation, and it has two kinds of precursors pulses of interspersed two kinds of purge gas;
Fig. 2 B describes a variant of ALD circulation, and it has two kinds of precursors pulses, and described pulse precursor is placed in gas and continues in the reaction chamber of purging;
Fig. 2 C describes in a typical CVD technique, the change of different process gas flow parameter;
Fig. 3 is the schema of a typical ALD processes, forms the film of desired thickness by the order of this technique;
Fig. 4 is a schema, and this figure describes the depositing system parameter of a typical CVD technique;
According to one embodiment of present invention, Fig. 5 A illustrates one by surface adsorption-OH group with the substrate of deposition;
According to one embodiment of present invention, Fig. 5 B illustrates by surface-OH groups chemisorption gas phase CCl 4molecule and by slough gas phase HCl molecule formed chemical bond;
According to one embodiment of present invention, Fig. 5 C illustrates silane (SiH on the surface of the substrate 4) CCl of molecule and front chemisorption 3the reaction occurred, permutoid reaction is with forming Si-C key and sloughing HCl and hydrogen atom formation face extremities;
According to one embodiment of present invention, Fig. 5 D illustrates that the first step that next ALD circulates starts from chemisorption CCl in H end surface 4and chemical bond is formed between Si and C;
According to one embodiment of present invention, Fig. 6 A is the change curve of Gibbs free energy (AG) relative to base reservoir temperature, this base reservoir temperature for make respectively as Si and C presoma SiH 4and CCl 4reaction generates SiC; With
According to one embodiment of present invention, Fig. 6 B is the change curve of Gibbs free energy (AG) relative to base reservoir temperature, this base reservoir temperature for make respectively as B and N presoma B 2h 6and NF 3reaction generates BN.
Embodiment
One provides low temperature depositing carbide, nitride and such as by the inventive method of ald (ALD), nanolayer deposition (NLD) and chemical vapour deposition (CVD) carbonitride mixed phase ceramic membrane.Compared to existing membrane deposition method, this sedimentation chemistry adopts presoma combination to affect the substantially lower temperature of thin-film technique, it is than the existing boron for various substrate (B), carbide, nitrogen (N), nitride, carbonitride of silicium (Si), carbon (C), germanium (Ge), phosphorus (P), arsenic (As), oxygen (O), sulphur (S), and the membrane deposition method of selenium (S) has substantially lower temperature.In embodiments of the inventive method, depositing temperature is preferably lower than 600 DEG C, and existing depositing operation carries out all at relatively high temperatures.Relative to NLD and CVD technique or method, ALD specific embodiment of the present invention provides lower temperature deposition for various film, and this film comprises the atomic group of B, C, Si, Ge, N, P, As, O, S and Se.
Precursors combination in the specific embodiment of deposition method of the present invention is selected based on reactivity each other, by the mensuration changed relative to the Gibbs free energy (△ G) of depositing temperature.The higher Gibbs free energy negative value of reaction is the basis of preferred reaction precursor combination.
For ALD and CVD technique, the active presoma of various element classifies (such as, hydride or halogenide) according to a type usually.But, be attached to that C, Si are upper, the another kind of type of the compound formation that comprises hydrogen and halogen.The thin film deposition processes of various material is implemented based on a class gas---and such as, a kind of hydride of element and the halide reaction of the second element are to having deposited vigorous reaction, and making to react clean Gibbs free energy (△ G) is negative value.In addition, if ternary or quaternary film, the hydride of one or more elements can combine with the halogenide of element needed for other.For ALD technique of the present invention, correspondingly selecting one or more hydride as the first precursors from comprising B, C, N, Si, Ge, P, O, S and Se Elements Atom group, selecting one or more halogenide of F, Cl, Br, I as the second precursors.Such as, nitrogen trifluoride (NF is adopted 3) as nitrogenous source, and adopt B2H6 as boron presoma.But under silicon carbide ALD technique, silicon source is selected from Si2H6, SiH4, SiH3X, SiH2X2 and SiHX3 (wherein X=F, Cl, Br and I), and carbon source is selected from CX 4, CX 3h, CX 2h 2and CX 3h (wherein X=F, Cl, Br and I).
In addition, mixing halocarbon, the Chlorofluorocarbons (wherein, n, a, b are integers, X and Z is halogen) such as with general formula CnXaZb is suitable for the carbon source as ALD, NLD and CVD technique research and development too.Another precursors subfraction comprises the mixed halide of C and Si, and its general formula is expressed as MnHaXb (M=C and Si; X=F, Cl, Br, I, N, A, b are integers).The preferred embodiment describe the various precursors combinations for developing multiple thin-film technique.
But it should be pointed out that with regard to the research and development of ALD thin-film technique, the first precursors can be a kind of halogenide or hydride, and corresponding second precursors is then a kind of hydride or halogenide.For the CVD technique of various material as carbide, nitride, silicide, sulfide, selenide, phosphide, arsenide and mixed phase thereof, adopt the same reaction thing combination used in the ald process to obtain required film composition.
In order to implement the embodiment of the inventive method, the various CVD reactor design be industrially widely used inject two kinds of reactant presomas respectively equably.Such ALD/CVD reactor and various being configured in the 6th, 812, No. 157 United States Patent (USP)s of full content incorporated herein by reference thereof are described.
In order to realize depositing operation of the present invention, need a kind of can change with Controlling Technology variable to carry out the technological reaction chamber of required chemical reaction.A hot-plate is set in this technological reaction chamber, makes temperature according to the requirement adjustment of particular deposition technique and can keep constant.The film substrate of required deposition is placed in the position with hot-plate thermo-contact, substrate is heated to predetermined temperature to produce required chemical reaction.This technological reaction chamber is also provided with the inlet mouth be connected with precursor gas supplying opening, and precursor gas is by suitable flow measurement and control valve supply.This technological reaction chamber is also connected on a vacuum pump, and this vacuum pump regulates the pressure of chamber by the throttling valve in downstream in deposition process.This technological reaction cavity pressure by constant adjustment downstream throttling valve synchronous with suction pulsation with keep constant or this pressure by the downstream throttling valve of a fixed position with gas pulses dynamic change.
Thin film deposition processes described in the invention in fact mainly atomize layer deposition (ALD) and chemical vapour deposition (CVD).In a classical ALD technique, presoma is sequentially added in technological reaction chamber, this reaction chamber has the continuous background air-flow of a sweeping gas or this two kinds of Purge gas pulses are interspersed in precursors, the ultimate principle of ALD technique and operate in the 4th, describe in 058, No. 430 United States Patent (USP)s.In chemical vapor deposition method, with a kind of all precursors gases of Purge gas with constant rate of speed simultaneously through to be heated substrate, wherein chamber pressure or and/or base reservoir temperature can adjust as required.
A kind of transitional type being referred to as the thin film deposition of nanolayer deposition has been commonly used to the technical process of omitting one or both gas pulses recently.In a NLD technique, reactant gases is alternately continuous flow usually, and therefore, precursors molecule forms chemical bond by following classes.But excessive response precursor molecule can not be cleared away near substrate surface, therefore under a pair gas pulses, more than thin film is formed.Should be understood that, also within the scope of the present invention, therefore this thin film deposition chemistry is based on to the choose reasonable of precursors disclosed herein and combination to NLD technique.
In addition, technique described herein---ALD, CVD or NLD effectively can carry out under normal atmosphere (760 holder) and the chamber pressure being low to moderate a few millitorr (mT).Therefore, the technological temperature of ALD or CVD technique also can different from other techniques, depend on multiple factors such as precursors composition, substrate type because of technological temperature to a great extent.Therefore, be necessary it is noted that be suitable for the non-constant width of Process temperature ranges---from room temperature to 1000 DEG C.
The described ALD technique prioritizing selection presoma that reactive behavior is high each other, is beneficial to effective operation of ALD technique.But, should be noted that, as long as before arrival substrate surface, enough effective dispersions carefully also uniformly distributing precursor flows, with the particle avoiding unnecessary pre-reaction and formed by means of suitable chamber design, then identical precursors composition also can be used for researching and developing corresponding CVD technique.In the ald process, the interaction between substrate surface and precursors is most important.Therefore, the character of precursors molecule in the stereospecificity of geometrical shape, size and peripheral activity group to realizing surface coverage excellence, film density is high and film total quality is high efficient ALD technique is very important.
Typically, ALD technique is surface elevation sensitivity, and be therefore injected into chemical precursors molecule on chamber substrate and the preadsorption substance reaction at substrate surface in a gaseous form, these materials are present in environment, are generally moisture (H 2o), CO, CO 2and N 2gas.But it should be noted that these four kinds are present in the gaseous species in environment, water molecules tends to and metal or nonmetallic surface atomic reaction, therefore easily provides the surface of employing OH group end capping as shown in Figure 1A.Suitable gaseous plasma, high temperature or high vacuum or their combined treatment surface can be adopted, change surface properties and its reactivity.
Therefore, the gaseous precursor molecules introduced, high TiCl as active in effects on surface-OH radical reaction 4, by with surface exchange Cl atom, to make it at surperficial O species and-TiCl 3between form chemical bond, thus carry out chemisorption.As shown in Figure 1B, in chemisorption process, release HCl molecule.In next step, the gas phase H introduced 2o molecular chemistry is adsorbed on-TiCl 3on the Cl group of group, thus form Ti-O key as shown in Figure 1 C.In this step, surface adopts-OH group end capping, and these-OH groups can accept next TiCl 4gaseous precursor pulse.Above-mentioned gaseous state pulse sequence does not introduce TiCl 4and H 2sweep gas pulse after O pulse.The main purpose of sweep gas pulse is cleaning physical adsorption or the loose excessive TiCl be attached on substrate 4and/or H 2o molecule.From above-mentioned discussion, for efficient ALD technique, be necessary the chemical precursors selecting reactive behavior each other high.That flux has nothing to do, be favourable based on the ALD technique of chemisorption, because it enormously simplify chamber design and technique in-house operation.But it also proposes substrate surface chemical property to acceptance (fixing) first chemical reaction precursor molecule start the ALD cycle to obtain the importance of target product.
Processing step described in Figure 1A-1C shows that an ALD cycle has four discrete pulses---the first reaction gas as shown in Figure 2 A, sweep gas, the second reaction gas and last sweep gas, then repeat this ALD cycle, to reach required film thickness.Alternatively, as shown in Figure 2 B, repeat subsequently at one, with in the ALD cycle reaching required film thickness degree, sweep gas flow constant in chamber, reaction gas pulse in time interts.In the ald process, when precursors pulse is on substrate, form key between surface species, therefore precursors is also referred to as chemical precursors, and reactive behavior is high each other.But, for chemical vapour deposition (CVD) technique, all precursor gas and sweep gas (main be used as thinner or ballast gas) with the substrate of constant rate of speed simultaneously by heating, wherein chamber pressure and/or underlayer temperature adjustable.Precursors and the inertia/gaseous purge stream timing variations (temperature, constant pressure) in a typical CVD technique as shown in Figure 2 C.
Fig. 3 shows the logical flow chart of the typical ALD processes step 10 with four discrete pulses.This technique is from being loaded in chamber 12 by substrate, and adjusting process parameter 14, comprise underlayer temperature, chamber pressure etc.Subsequently, an ALD cycle, from the first precursors gas pulse 16, is then sweep gas pulse 18, second precursors pulse 20, afterwards chamber is introduced in sweep gas pulse 22.Judge whether the coating of deposited on substrates reaches predetermined thickness 24 afterwards.If reached predetermined coat-thickness, then stop this technique 26.If but the coat-thickness on substrate not yet reaches predetermined coat-thickness, then repeat the gaseous state pulse of step 16-22 in the ALD cycle, until reach predetermined thickness.
Fig. 4 shows the logical flow chart of typical ALD processes 30.This technique is from being loaded in chamber 32 by substrate, and adjusting process parameter 44, comprise underlayer temperature, chamber pressure etc.Then, the CVD cycle, from rare gas element is introduced chamber 36, introduces the first precursors air-flow 38 subsequently, starts the second presoma air-flow subsequently and keeps the first presoma air-flow 40 in chamber.Judge whether the coating of deposited on substrates reaches predetermined thickness 42.If reached predetermined coat-thickness, then stop this technique 44.If but the coat-thickness on substrate not yet reaches predetermined coat-thickness, then repeat the gaseous state pulse of step 36-40 in the CVD cycle, until reach predetermined thickness.
In the embodiment of depositing operation of the present invention, selecting the halogenide comprising B, C, Si, Ge, N, P, As, S and Se element as one group of compound of the first precursors, obtaining required film by adopting ALD, NLD and CVD technique.Second precursors of ALD, NLD and CVD technique is selected from the halogenide comprising B, C, Si, Ge, N, P, As, O, S and Se element.Therefore the representative compound of these elements is selected from and includes, but are not limited to B 2h 6, CH 4, SiH 4, Si 2h 6, NH 3, N 2h 4, PH 3, AsH 3, H 2o, H 2s and H 2the compound of Se.Another subclass comprising the precursors of C and Si also comprises and is designated as general formula C nx' ax " b(X=F, CI, Br and I; N, a and b are integer) mixture of halides.Another subclass of precursors also comprises and is designated as formula M nh ax b(M=C, Si; X=F, Cl, Br, I, n, a, b are integer) the mixture of halides of C and Si.Preferred embodiment describes the multiple combination of precursors, can be used for researching and developing multiple thin-film technique.
The embodiment of the present invention is set forth further by example hereinafter described and correlation graph.
embodiment 1
Adopt ALD, NLD and CVD process deposits silicon carbide (SiC) film: as described in background technology part of the present invention, SiC is a kind of widely used essential industry pottery.But general SiC thin film deposition processes is carried out at the temperature more than 1000 DEG C.Therefore, in the urgent need to a kind of SiC thin film low temperature ALD, CVD technique.With reference to Fig. 5 A, substrate surface adopts-OH group end capping, and the acceptant Cl atom of-OH group also has high reaction activity to Cl atom.Then, in figure 5b, wherein, tetracol phenixin (CCl is completed 4) molecule (TiCl described with Figure 1B 4molecular mimicry) chemisorption on the substrate surface of-OH end-blocking, form HCl product, HCl discharges in a gaseous form.At CCl 4at the end of chemisorption step, substrate is to form M-O-CC1 3(M: the surface atom of substrate, is expressed as square in Fig. 5 A, B, C and D) key is with Cl group end capping.Then, sweep gas pulse (not shown) is introduced this technique, the unnecessary CCl of cleaning substrate proximity 4molecule.Subsequently, by silane (SiH 4) gas pulses introduces in chamber.As shown in Figure 5 C ,-the O-CCl of silane gas molecule and chemisorption 3group is vigorous reaction under the process conditions, and forms Si-C key, removing HCl molecule.Sweep gas pulse is for removing excessive SiH 4molecule (not shown).As shown in Figure 5 D, substrate surface, with H atom end-blocking, therefore can accept next CCl 4input pulse.The total reaction of SiC deposition is as follows:
CCl 4+ SiH 4→ SiC+4HCl equation (1)
Fig. 6 A shows the Gibbs free energy (Δ G) of reaction shown in equation (1) relative to the changing conditions of temperature and the contrast situation with traditional Si CCVD technique thereof.In Fig. 6 A, relative to technological temperature (even room temperature), Δ G negative value is high, shows the very high potential of low temperature SiC depositing operation (ALD or CVD) feasibility shown in equation (1).
Should be understood that above-mentioned SiCALD technique not by the restriction of process chamber pressure, therefore this technique can be carried out under the wide region operation pressure even higher to 760 holders (1 normal atmosphere) from a few millitorr.In addition, described SiCALD technique also can such as carried out from the wide temperature range of room temperature to 1000 DEG C.In addition, the sedimentation chemistry equation described in equation (1) is equally applicable to corresponding CVD and NLD technique.
embodiment 2
The thin-film material that another kind has industrial value is boron nitride (BN).Current use BCl 3with ammonia (NH 3) under the hot conditions of 700 ~ 1000 DEG C and above temperature, deposit BN film.Fig. 6 B shows the change of Gibbs free energy (Δ G) relative to temperature of following chemical reaction:
B 2h 6+ 2NF 3→ 2BN+6HF equation (2)
Compared with traditional B N technique (ALD or CVD), the Δ G in reaction shown in equation (2) is very large relative to the value of temperature, describes the high level needed for exploitation low temperature BN thin film deposition processes.BN depositing operation can carry out under the pressure condition from several mT to 760Torr and from the temperature condition of 20 DEG C to 1000 DEG C.
embodiment 3
C 3n 4the deposition of film: C 3n 4also not yet fully developed as the depositing operation of thin-film material and various application.It is expected to become one of known superhard material.C 3n 4the formation of film adopts ALD, NLD or CVD technique, with carbon halogenide (such as CF 4, CF 2cl 2or CC1 4) be carbon source, with NH 3for nitrogenous source, in temperature range from 20 DEG C to 1000 DEG C, pressure range is carry out under the condition of several mT to 760Torr.Total chemical reaction of deposition is (with CC1 4for carbon source) as follows:
3CF 4+ 4NH 3→ C 3n 4+ 12HF equation (3)
embodiment 4
The deposition of Si3N4 film: silicon nitride is important industrial ceramics, because silicon nitride has the anticorrosive of excellent optical performance and high-abrasive material.Silicon nitride can be applicable to spot contact bearing coating and electrical insulator, antireflecting coating etc.Si 3n 4the formation of film adopts ALD, NLD or CVD technique, with silane (SiH 4) be silicon source, NF 3for nitrogenous source carries out.Si 3n 4total chemical reaction of deposition is as follows:
3SiH 4+ 4NF 3→ Si 3n 4+ 12HF equation (4)
embodiment 5
Si xge (1_X)the deposition of film: Si xge (1_X)film can adopt ALD, NLD or CVD technique, uses the hydride of Si and the halogenide of Ge to deposit.First reactant gases pulse comprises with SiCl 4and GeCl 4fixing ratio be the mixture of a:b, this mixture generate with first individual layer comprising Si atom and Ge atom of Cl group end capping.Second reactant gases pulse comprises with GeH 4and SiH 4fixing ratio be the mixture of a:b, and the x value that can be fixed.Si xge (1_X)the total reaction of depositing operation can be write (the non-trim of equation):
(SiCl 4+ GeCl 4)+(SiH 4+ GeH 4) → Si xge (1_X)+ HCl equation (5)
Wherein, round bracket represents pulse group.A kind of optional method of the Si:Ge of adjustment ratio uses silane or Germane gas specially as the second precursors.The reaction of ALD technique is as follows:
(SiCl 4+ GeCl 4)+SiH 4→ Si xge (1_X)+ HCl equation (6)
Process Production Si-rich phase (higher x value) described by equation (6).On the other hand, GeH is used 4rich germanium phase as generating during the second precursors described by equation (7):
(SiCl 4+ GeCl 4)+GeH 4→ SiXGe (1_X)+ HCl equation (7)
In addition, film Si xge (1_X)in Si:Ge ratio (x value) also by change change as the processing condition such as base reservoir temperature and pulse width.
embodiment 6
Various material is (as SiC xthe deposition of ternary film Ny), adopts ALD, NLD or CVD technique, uses SiH 4as the first reactant gases pulse, be combined CCl 4(CF of equivalence can be selected 4) and NF 3mixture carries out as the second reactant gases pulse.
(SiH 4)+(CCl 4+ NF 3) → SiC xn y+ HCl equation (8)
embodiment 7
Quaternary film can adopt ALD, NLD or CVD technique, uses the mixture of hydride in the first pulse, in the second pulse, use halid mixture.Such as, SiC xb yn zdeposition can use and comprise silicomethane (SiH 4) and diborane (B 2h 6) the first reaction precursor gaseous mixture, use comprise tetracol phenixin (CCl 4) and nitrogen trifluoride (NF 3) the second reaction precursor gaseous mixture, total chemical reaction is as shown in equation (9):
(SiH 4+ B 2h 6)+(CCl 4+ NF 3) → SiC xb yn z+ HCl+HF equation (9)
embodiment 8
C film: ALD, NLD or CVD technique of thin film containing carbon uses multiple precursors composition and carries out.Most important precursors composition is general formula is CH 2x 2the two chloro-halid pulses of (X=F, Cl, Br and I), total chemical reaction is as shown in equation (10):
CH 2x 2+ CH 2x 2→ C+2HX equation (10)
Or, with CX 4(X=F, Cl, Br and I) is the first precursors, with CH 4be second answer presoma be equally applicable to deposit carbon film, total chemical reaction is as shown in equation (11).
CX 4+ CH 4→ C+4HX equation (11)
embodiment 9
Use silane containing hydrogen and borane reduction halo carbon Formed individual layer: in the ald process, known to silane (SiH 4) and silicoethane (Si 2h 6) to be used at temperature range is 200 ~ 400 DEG C as reductive agent and to deposit the metals such as such as tungsten, reaction formula is as follows:
WF 6+ SiH 4→ W+SiF 4+ 2HF+H 2equation (12)
WF 6+ Si2H 6→ W+2SiHF 3+ 2H 2equation (13)
Reference:
(a) J.W.Elam, C.E.Nelson, R.K.Grubbs and S.M.George, ThinSolidFilms, calendar year 2001, the 386th volume, the 41st page.
(b) JournalofVacuumScience & Technology (B), in July, 2004, the 22nd volume the 4th phase, 1811-1821 page.
Correspondingly, reduction CCl 4, such as, in temperature range to be the C film depositing variform under the condition of 200 ~ 800 DEG C, decolorizing carbon or Graphene.Total reaction can be summarized as:
CCl 4+ SiH 4→ C+SiCl 4+ 2H 2equation (14)
CCl 4+ SiH 4→ C+SiH 2cl 2+ 2HCl equation (15)
CCl 4+ Si2H 6→ C+Si 2h 2cl 4+ 3H 2equation (16)
Also diborane (B can be used 2h 6) substitute silicoethane promotes carbon or graphene film deposition total reaction as reductive agent.
Description is above the explanation to specific embodiment of the present invention, but this and do not mean that restriction enforcement of the present invention.Claim below, comprises its all equivalent form of value, is intended to limit scope of the present invention.

Claims (14)

1., for a method for the ceramic membrane coating of low temperature depositing carbide, nitride and mixed phase thereof, described method comprises:
Determine sedimentation chemistry composition, this composition uses precursors composition with impact by temperature required at substrate surface of described thin film deposition;
Described substrate is loaded into chamber;
Regulate one or more processing parameter, comprise base reservoir temperature, chamber pressure and chamber temp;
Start deposition cycle (cycle);
Determine whether the pre-determined thickness reaching described film coating, and repeat described deposition cycle until reach described pre-determined thickness;
Wherein said deposition adopts ald (ALD), nanolayer deposition (NLD) or chemical vapour deposition (CVD);
Wherein select described precursors composition based on the reactive behavior between each described precursors, the Gibbs free energy (Δ G) that described reactive behavior is changed by the depositing temperature with described chamber is determined.
2. method according to claim 1, it is characterized in that, described film comprises boron (B) carbide, nitrogen (N), nitride, the carbonitride of silicon (Si), carbon (C), germanium (Ge), phosphorus (P), arsenic (As), oxygen (O), sulphur (S), selenium (S).
3. method according to claim 1, is characterized in that, the reaction Gibbs free energy of higher negative value is the selection foundation basis of described precursors composition.
4. method according to claim 1, is characterized in that, the described precursors of multiple element is classified, for described ALD and described CVD technique according to hydride or halogenide usually.
5. method according to claim 4, it is characterized in that, from the first element and the vigorous reaction affecting deposition from described halid second element reaction of described hydride, to make the clean Gibbs free energy (Δ G) of reacting be negative value.
6. method according to claim 5, is characterized in that, described first element is selected from the group of the hydride comprising B, C, N, Si, Ge, P, O, As, S and Se; And
Wherein said second element is selected from halid group that comprises F, Cl, Br or I.
7. method according to claim 6, is characterized in that, uses nitrogen trifluoride (NF 3) as a kind of nitrogenous source, and in conjunction with B 2h 6as a kind of boron presoma.
8. method according to claim 6, is characterized in that, described ALD technique is the technique based on silicon chlorides, and silicon source is selected from Si 2h 6, SiH 4, SiH 3x, SiH 2x 2and SiHX 3, wherein X is F, Cl, Br or I independently when occurring at every turn; And carbon source is selected from CX 4, CX 3h, CX 2h 2and CX 3h, wherein X is F, Cl, Br or I independently when occurring at every turn.
9. method according to claim 6, is characterized in that, halo carbon mixture is a kind of carbon source.
10. method according to claim 9, is characterized in that, described halo carbon mixture has general formula C nx az bchloro-fluoro-carbon compound, wherein n, a and b are integer and X and Z is halogen.
11. methods according to claim 6, is characterized in that, described halogenide comprises further uses formula M nh ax bthe mixture of halides subclass (sub-class) of C and Si represented, wherein M=C, Si, X are F, Cl, Br or I when occurring at every turn independently, and n, a and b are integer.
12. methods according to claim 1, is characterized in that, described chamber pressure scope is from normal atmosphere (760Torr) to being low to moderate 1 millitorr (mT).
13. methods according to claim 1, is characterized in that, described method comprises described surface silicon carbide film being deposited on the described substrate using-OH group end capping further, and-OH group has high acceptable and reactive behavior to Cl atom;
Introduce tetracol phenixin (CCl 4) molecule, chemisorption on the substrate surface at-OH end-blocking, to generate O-CCl 3group;
Purge gas is sent into described chamber, to purge the excessive CCl near described substrate 4molecule;
By silicomethane (SiH 4) gas pulses introduces described chamber, makes-the O-CCl of itself and described chemical adsorption states 3radical reaction, generates Si-C key;
Described purge gas is to remove excessive SiH 4molecule, makes described surface with hydrogen (H) end-blocking, this can accept the CCl entered with the surface of hydrogen (H) end-blocking 4pulse; And
The total reaction of wherein said SiC deposition is CCl 4+ SiH 4→ SiC+4HCl.
14. films prepared by any one of claim 1 ~ 13 method.
CN201480010010.1A 2012-12-21 2014-01-01 Methods of low temperature deposition of ceramic thin films Pending CN105143503A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261745523P 2012-12-21 2012-12-21
PCT/IB2014/000001 WO2014097280A1 (en) 2012-12-21 2014-01-01 Methods of low temperature deposition of ceramic thin films

Publications (1)

Publication Number Publication Date
CN105143503A true CN105143503A (en) 2015-12-09

Family

ID=50977720

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480010010.1A Pending CN105143503A (en) 2012-12-21 2014-01-01 Methods of low temperature deposition of ceramic thin films

Country Status (5)

Country Link
US (1) US20150329965A1 (en)
EP (1) EP2935646A4 (en)
JP (1) JP2016507001A (en)
CN (1) CN105143503A (en)
WO (1) WO2014097280A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111429976A (en) * 2020-03-24 2020-07-17 上海交通大学 Optimized screening system and method for reaction flux for directionally removing impurities in molten metal

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10325773B2 (en) 2012-06-12 2019-06-18 Novellus Systems, Inc. Conformal deposition of silicon carbide films
US9234276B2 (en) 2013-05-31 2016-01-12 Novellus Systems, Inc. Method to obtain SiC class of films of desired composition and film properties
US10763103B2 (en) * 2015-03-31 2020-09-01 Versum Materials Us, Llc Boron-containing compounds, compositions, and methods for the deposition of a boron containing films
KR101704723B1 (en) * 2015-04-06 2017-02-09 연세대학교 산학협력단 Carbon thin-film device and method for manufacturing the same
GB201514542D0 (en) * 2015-08-14 2015-09-30 Thomas Simon C S A method of producing graphene
US10388515B2 (en) * 2015-11-16 2019-08-20 Taiwan Semiconductor Manufacturing Company, Ltd. Treatment to control deposition rate
TW201822259A (en) * 2016-09-09 2018-06-16 美商諾發系統有限公司 Remote plasma based deposition of oxygen doped silicon carbide films
US10745803B2 (en) * 2017-06-15 2020-08-18 Rolls-Royce High Temperature Composites Inc. Method of forming a moisture-tolerant coating on a silicon carbide fiber
CN111295465B (en) * 2017-09-14 2022-12-09 弗萨姆材料美国有限责任公司 Compositions and methods for depositing silicon-containing films
KR20200127261A (en) * 2018-03-26 2020-11-10 램 리써치 코포레이션 Atomic layer deposition of carbon films
WO2020081367A1 (en) 2018-10-19 2020-04-23 Lam Research Corporation Doped or undoped silicon carbide deposition and remote hydrogen plasma exposure for gapfill
JP6783888B2 (en) * 2019-03-15 2020-11-11 株式会社Ｋｏｋｕｓａｉ Ｅｌｅｃｔｒｉｃ Manufacturing method of semiconductor devices, substrate processing devices and recording media
CN111597735B (en) * 2020-06-19 2022-06-14 华南理工大学 Component prediction method combining machine learning and CVD modeling

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4720395A (en) * 1986-08-25 1988-01-19 Anicon, Inc. Low temperature silicon nitride CVD process
EP0442490A1 (en) * 1990-02-14 1991-08-21 Sumitomo Electric Industries, Ltd. Method for producing single crystal boron nitride film
US5196366A (en) * 1989-08-17 1993-03-23 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing electric devices
JPH06135711A (en) * 1992-03-10 1994-05-17 Semiconductor Energy Lab Co Ltd Production of silicon carbide film
EP1149934A2 (en) * 2000-04-28 2001-10-31 Asm Japan K.K. CVD synthesis of silicon nitride materials
US20030203614A1 (en) * 2002-04-29 2003-10-30 Applied Materials, Inc. Method for forming silicon containing layers on a substrate
CN101199044A (en) * 2005-06-17 2008-06-11 应用材料股份有限公司 Method for silicon based dielectric chemical vapor deposition
US20110256734A1 (en) * 2010-04-15 2011-10-20 Hausmann Dennis M Silicon nitride films and methods
CN102304701A (en) * 2011-09-26 2012-01-04 中国科学院微电子研究所 Preparation method of silicon carbide film
US20120177841A1 (en) * 2010-09-24 2012-07-12 Applied Materials, Inc. Low Temperature Silicon Carbide Deposition Process

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6357772A (en) * 1986-08-26 1988-03-12 Matsushita Electric Ind Co Ltd Preparation of silicon carbide film
JPH10114586A (en) * 1996-10-04 1998-05-06 Fine Ceramics Center Production of composite material coated with ceramics
US20030059535A1 (en) * 2001-09-25 2003-03-27 Lee Luo Cycling deposition of low temperature films in a cold wall single wafer process chamber
JP4257576B2 (en) * 2003-03-25 2009-04-22 ローム株式会社 Deposition equipment
US7404858B2 (en) * 2005-09-16 2008-07-29 Mississippi State University Method for epitaxial growth of silicon carbide
US7572052B2 (en) * 2007-07-10 2009-08-11 Applied Materials, Inc. Method for monitoring and calibrating temperature in semiconductor processing chambers
US8221546B2 (en) * 2008-03-26 2012-07-17 Ss Sc Ip, Llc Epitaxial growth on low degree off-axis SiC substrates and semiconductor devices made thereby
US9611544B2 (en) * 2010-04-15 2017-04-04 Novellus Systems, Inc. Plasma activated conformal dielectric film deposition
KR101975071B1 (en) * 2011-09-23 2019-05-03 노벨러스 시스템즈, 인코포레이티드 Plasma activated conformal dielectric film deposition

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4720395A (en) * 1986-08-25 1988-01-19 Anicon, Inc. Low temperature silicon nitride CVD process
US5196366A (en) * 1989-08-17 1993-03-23 Semiconductor Energy Laboratory Co., Ltd. Method of manufacturing electric devices
EP0442490A1 (en) * 1990-02-14 1991-08-21 Sumitomo Electric Industries, Ltd. Method for producing single crystal boron nitride film
JPH06135711A (en) * 1992-03-10 1994-05-17 Semiconductor Energy Lab Co Ltd Production of silicon carbide film
EP1149934A2 (en) * 2000-04-28 2001-10-31 Asm Japan K.K. CVD synthesis of silicon nitride materials
US20030203614A1 (en) * 2002-04-29 2003-10-30 Applied Materials, Inc. Method for forming silicon containing layers on a substrate
CN101199044A (en) * 2005-06-17 2008-06-11 应用材料股份有限公司 Method for silicon based dielectric chemical vapor deposition
US20110256734A1 (en) * 2010-04-15 2011-10-20 Hausmann Dennis M Silicon nitride films and methods
US20120177841A1 (en) * 2010-09-24 2012-07-12 Applied Materials, Inc. Low Temperature Silicon Carbide Deposition Process
CN102304701A (en) * 2011-09-26 2012-01-04 中国科学院微电子研究所 Preparation method of silicon carbide film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111429976A (en) * 2020-03-24 2020-07-17 上海交通大学 Optimized screening system and method for reaction flux for directionally removing impurities in molten metal
CN111429976B (en) * 2020-03-24 2023-04-18 上海交通大学 Optimized screening system and method for reaction flux for directionally removing impurities in molten metal

Also Published As

Publication number Publication date
WO2014097280A1 (en) 2014-06-26
EP2935646A1 (en) 2015-10-28
US20150329965A1 (en) 2015-11-19
EP2935646A4 (en) 2016-10-12
JP2016507001A (en) 2016-03-07

Similar Documents

Publication Publication Date Title
CN105143503A (en) Methods of low temperature deposition of ceramic thin films
US20210292902A1 (en) Method of depositing epitaxial material, structure formed using the method, and system for performing the method
US20210102290A1 (en) Gas injection system and reactor system including same
US10167549B2 (en) Heat-resistant composite material production method and production device
CN101228292B (en) Method for silicon nitride chemical vapor deposition
WO2014027472A1 (en) Method for manufacturing heat resistant composite material and manufacturing device
CN108026637A (en) Method for depositing conformal metal or metalloid silicon nitride films and resulting films
KR20000071446A (en) Method and manufacturing device for manufacturing a titanium nitride thin film
CN102471885A (en) Metal nitride containing film deposition using combination of amino-metal and halogenated metal precursors
JPH07147251A (en) Growth of crystalline silicon carbide film
JP2011522120A5 (en)
CN104412362B (en) Silicon carbide epitaxy chip and preparation method thereof
Ovanesyan et al. A Three-Step Atomic Layer Deposition Process for SiN x Using Si2Cl6, CH3NH2, and N2 Plasma
Carlsson Processes in interfacial zones during chemical vapour deposition: aspects of kinetics, mechanisms, adhesion and substrate atom transport
Lu et al. Kinetics of chemical vapor deposition of SiC from methyltrichlorosilane and hydrogen
JP6637095B2 (en) Low temperature deposition method of ceramic thin film
JP2006096675A (en) New amino-disilane and method for forming silicon carbonitride film
Fukushima et al. Multiscale analysis of silicon carbide-chemical vapor deposition process
Yan et al. Kinetic and microstructure of SiC deposited from SiCl4-CH4-H2
CN107492483A (en) A kind of growth of silicon carbide method in mixed growth source
Yang et al. Chemical vapor deposition of SiC at different molar ratios of hydrogen to methyltrichlorosilane
KR101916289B1 (en) Method for deposition of silicon carbide
US20150144963A1 (en) Silicon carbide epi-wafer and method of fabricating the same
KR102203025B1 (en) Method of fabricating silicone carbide epi wafer
KR20130065945A (en) Method for deposition of silicon carbide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20151209